JP2000247690A - Adhesive intermediate film for laminated glass and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an intermediate film having high transparency, excellent water resistance and good adhesion property for a wide variety of materials having various kinds of functions, good handling property and excellent resistance against a plasticizer by incorporating a partially saponified ethylene-vinyl acetate copolymer or its acid modified product, rosins and a plasticizer. SOLUTION: The ethylene-vinyl acetate copolymer used has 25 to 70 wt.% of a vinyl acetate content, and its melt index is 0.1 to 500. The saponification degree of the partially saponified copolymer (HEVA) is controlled to 30 to 90 mol%. To modify HEVA with an acid, an unsatd. carboxylic acid (e.g. acrylic acid) is used. The amt. of the acid used is 0.1 to 15 wt.% to the weight of HEVA. The amt. of rosins (e.g. water-added rosin) is 2 to 20 pts.wt. to 100 pts.wt. of HEVA. As for a plasticizer, for example, dioctylphthalate is used by 0.5 to 10 pts.wt. to 100 pts.wt. of HEVA.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive interlayer for laminated glass having excellent transparency, adhesion, durability and plasticity, and a laminated glass using the same.

[0002]

2. Description of the Related Art Conventionally, laminated glass is used to prevent breakage, prevent danger due to breakage, enhance security, impart decorativeness,
It is widely used in automobiles, aircraft, vehicles, buildings, office automation equipment, and the like for the purpose of imparting various functions such as improvement in soundproofing.
As the adhesive intermediate film used in the production of the laminated glass, an acid-modified product of a partially saponified product of a conventionally plasticized polyvinyl butyral and an ethylene-vinyl acetate copolymer (hereinafter referred to as HE)
Sometimes referred to as VA-C. ), Cross-linked EVA, polyurethane, polyvinyl chloride, acrylic resin, etc. are used, but each has its advantages and disadvantages, and none of them are satisfactory for all uses. For example, plasticized polyvinyl butyral has excellent transparency and is widely used for automobiles and construction, but has poor water resistance, and has poor adhesion to acrylic or polycarbonate glass plates. It cannot be used for laminated glass.
Further, the polyvinyl butyral film has a disadvantage that it is difficult to handle at the time of use because it has adhesiveness itself. On the other hand, since HEVA-C has excellent water resistance and can be applied to any material, it is widely used for various functional laminated glass and laminated glass using various synthetic resin plates, but the adhesiveness is not always sufficient. It is not used for windshields of automobiles because of its poor transparency. When a laminated glass is used as a window glass of a building or an automobile, the laminated glass is manufactured by applying a buffer material such as putty, rubber, or a glazing gasket to a cut end of the laminated glass and combining it with a window frame. Since most of this buffer material contains a plasticizer, if the buffer material is in contact with the intermediate film exposed at the cut end of the laminated glass,
The interlayer absorbs the plasticizer contained in the cushioning material and swells, and peels off the laminated glass to impair the aesthetic appearance. Existing interlayers made of other resins are only slightly used for special purposes.

[0003]

Under these circumstances, it has been found that a material having various functions can be solved by eliminating the drawbacks of the above-mentioned conventional interlayer film, maintaining high transparency, having excellent water resistance. There is a strong demand for the development of an adhesive interlayer for laminated glass that exhibits a wide range of good adhesiveness, is easy to handle, and has excellent plasticizer resistance.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors, in particular, partially saponified ethylene-vinyl acetate copolymer (hereinafter sometimes referred to as HEVA) or as an intermediate film. Focusing on the acid-modified product, adding a rosin as a transparency modifier to it gives the same level of transparency as glass itself, and adding a certain amount of plasticizer to it will increase the plasticity in the buffer. The research has shown that laminated glass with excellent plasticizer resistance and durability can be obtained by preventing the transfer of the agent to the interlayer, preventing the interlayer from swelling and exfoliating the glass, and conducting further research. Completed the invention. That is, the present invention relates to (1) 100 parts by weight of a partially saponified ethylene-vinyl acetate copolymer or an acid-modified product thereof,
(1) an adhesive interlayer film for laminated glass containing from 0.5 to 20 parts by weight and a plasticizer from 0.5 to 10 parts by weight; and (2) an adhesive interlayer containing from 0.05 to 3 parts by weight of a silane coupling agent. And (3) a laminated glass bonded using the adhesive interlayer film for laminated glass according to the above (1) or (2).

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, HEV used in the present invention
A and HEVA-C will be described. Both of these compounds are known per se (for example, Japanese Patent Publication No. Sho 62-62).
No. 034043). The ethylene-vinyl acetate copolymer (hereinafter sometimes referred to as EVA) as a raw material for producing HEVA and HEVA-C usually has a vinyl acetate content of 25 to 70% by weight. Preferably, the content is 30 to 60% by weight.
Such an EVA can be produced by a known production method such as a high-pressure method or an emulsification method, and its melt index (g / 10 minutes (190 ° C., 2,106 g): AS
According to TM 1238-65T. Hereinafter the same)
500, preferably 1 to 300 can be used. The raw material EVA is then subjected to a saponification reaction to obtain a partially saponified EVA (HEVA).
The saponification degree is usually 30 to 90 mol%, preferably 40 to 8 mol%.
It is 5 mol%, more preferably 45 to 80 mol%. The saponification reaction may be performed by a method known per se. For example,
EVA can be dissolved in a solvent such as toluene or xylene, and can be carried out in a system comprising a low-boiling alcohol such as methanol or ethanol and an alkali such as sodium hydroxide, potassium hydroxide or sodium methylate.

Next, HEVA-C having a carboxyl group can be produced using this HEVA. H
Methods for acid-modifying EVA include a method using a graft reaction and a method using an esterification reaction. In order to utilize the graft reaction, it is usually carried out using an unsaturated carboxylic acid. Examples of such unsaturated carboxylic acids include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and itaconic acid, and unsaturated dicarboxylic acids (or anhydrides) such as maleic acid. Usually, acrylic acid is used. The grafting reaction is performed by benzoyl peroxide, lauroyl peroxide, α, α'-
The reaction may be carried out under known reaction conditions using a radical initiator such as azobisisobutyronitrile. The amount of the unsaturated carboxylic acid used is 0.1 to 1 based on the weight of HEVA.
It is 5% by weight, preferably 0.5 to 5% by weight. The acid value of the modified product having a carboxyl group obtained by such a reaction is usually 0.1 to 40, preferably 0.5 to 15
It is. When an esterification reaction is used, a dicarboxylic anhydride or the like is usually used. The reaction is carried out under esterification conditions known per se.

[0007] Such dicarboxylic anhydrides include:
Saturated or unsaturated maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, etc. Saturated, aliphatic, aromatic and alicyclic acid anhydrides can also be mentioned. The amount of the dicarboxylic anhydride to be used is an amount necessary for esterifying 5 to 60 mol%, preferably 10 to 50 mol%, of the hydroxyl groups in HEVA. The acid value of the thus obtained modified product having a carboxyl group is usually 10 to 200, preferably 2 to 200.
0 to 150. In the present invention, rosins are used as a transparency modifier. Rosins are thermoplastic resins containing abietic acid as a main component and include gum rosin, wood rosin, tall oil rosin and the like. Specifically, modified rosins such as hydrogenated rosin (dihydroabietic acid, tetrahydroabietic acid), disproportionated rosin, disproportionated hydrogenated rosin, polymerized rosin (including partially polymerized rosin), rosin or modified rosin And rosin-modified polyesters in which rosin or modified rosin is used as a part of the acid of the polyester, and alkyl esters, glycol esters, glycerin esters, pentaerythritol esters, and the like. Such a rosin-modified polyester can also be obtained by reacting a rosin or a glycidyl ester of a modified rosin with a carboxylic acid-containing compound.

The amount of rosin used in the present invention is HEV
It is usually in the range of 2 to 20 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the total amount of A or HEVA-C. Conventionally, a plasticizer is added to a resin for the purpose of exhibiting useful properties (flexibility, processability, etc.) that cannot be obtained with the resin alone (Japanese Patent Laid-Open No. 3-109241). For example, for plasticizing a polyvinyl chloride resin, a large amount of a plasticizer of 35 to 60 parts by weight is added to 100 parts by weight of polyvinyl chloride, and the mixture is kneaded and molded to produce a soft product. The plasticizer in the present invention is not added to impart properties such as flexibility and processability to the resin, but the plasticizer contained in the buffer material in contact is absorbed by the interlayer and the laminated glass is peeled off. It is added in a small amount for the purpose of preventing the occurrence of slag. Examples of such a cushioning material include a setting block, a backup material, an elastic sealing material such as a sealing material, a glazing channel, and a glazing gasket such as a glazing bead. Further, in the present invention, not only the separation of the laminated glass due to the transfer of the plasticizer contained in the buffer material to the intermediate film is suppressed, but also the acetic acid, oxime, alcohol and the like generated when the sealing material is cured are absorbed by the intermediate film. It is also possible to prevent the laminated glass from peeling off.

As the plasticizer used in the present invention, dioctyl phthalate (DOP), dibutyl phthalate (DB)
P), phthalic acid esters such as diisodecyl phthalate (DIPI), ditridecyl phthalate (DTDP) and butylbenzyl phthalate (BBP), trioctyl phosphate (TOP), tricresyl phosphate (TC
And phosphoric acid esters such as P). The amount of the plasticizer used is 0.5 to 10 parts by weight, preferably 3 to 7 parts by weight, based on 100 parts by weight of HEVA or HEVA-C. Further, in the present invention, by further blending a silane coupling agent with the above composition, an intermediate film having more excellent water resistance can be obtained. Epoxy silane, amino silane, and vinyl silane are used as the silane coupling agent. Particularly, epoxy silane, for example, γ-
Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. The silane coupling agent is usually 0.05 to 3 parts by weight based on 100 parts by weight of HEVA or HEVA-C.
Preferably, 0.1 to 1.0 part by weight is used. If necessary, a stabilizer, an ultraviolet absorber, a coloring agent, a dye, and a surfactant may be added.

In order to produce the interlayer according to the present invention, the components are usually melt-blended by an extruder, a kneader or the like, and then formed into a sheet using a T-die or the like.
The temperature condition at the time of forming the sheet is usually about 100 to 150 ° C. for pelletizing by an extruder, and about 100 to 180 ° C. for forming a film by a T-die. Further, the sheet may be formed using a calendar roll. This sheeting itself can be carried out by a known means (JP-A-60-171253). The thickness of the sheet is usually 50 to 2,000 μm, preferably 100 to 1.0.
00 μm. The surface of the sheet is preferably uneven in order to prevent bubbles from remaining during the production of the laminated glass, and it is preferable to add a satin pattern or an embossed pattern using an embossing roll or the like. For the production of the laminated glass, a generally known method, for example, a vacuum heat compression method, a thermocompression method, a method using an autoclave, or the like can be suitably used. The laminated glass in the present invention is obtained by bonding a glass-like transparent body such as an inorganic glass, a template glass, a polycarbonate resin, and an acrylic resin with an adhesive synthetic resin interlayer. In addition, one in which one of the superposed ones is a transparent resin film is also included. At that time, the laminated glass may be a flat plate or a glass having a curved surface. Also, a laminated glass in which a functional film having decorativeness, functionality, and the like is sealed is included. In this case, the intermediate film is used between the glass and the functional film or between the functional film and the functional film. For example, the structure of the laminated glass is glass / intermediate film / functional film / intermediate film / glass. A great variety of functional films for imparting such decorativeness and functionality have been developed. For example, various printed polyester films, bark (plated), cloth, paper, wire mesh, liquid crystal films, polarizing films, Examples include a conductive film and a silicone element.

[0011]

Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. Example 1 Pentaerythritol ester of completely hydrogenated rosin was added to 100 parts by weight of a carboxyl modified product of a saponified ethylene-vinyl acetate copolymer (melt index: 20 g / 10 min, Dumilan C-1550, manufactured by Takeda Pharmaceutical Co., Ltd.) 2
Parts by weight and 0.5 parts by weight of dioctyl phthalate are uniformly dispersed and formed into a film having a thickness of 0.25 mm. The film is sandwiched between two 3 mm-thick ordinary plate glasses (100 mm x 50 mm), the air bubbles between the layers are degassed, heated to about 100 ° C, and the whole is brought into close contact with an adhesive pressure of 1 atm to form a laminated glass. Manufactured.

Example 2 Completely hydrogenated rosin was added to 100 parts by weight of a carboxyl modified product of a saponified ethylene-vinyl acetate copolymer (melt index: 20 g / 10 min, Dumilan C-1550, manufactured by Takeda Pharmaceutical Co., Ltd.). Pentaerythritol ester 5
Parts by weight and 3 parts by weight of dioctyl phthalate are uniformly dispersed and formed into a film having a thickness of 0.25 mm. The film was treated in the same manner as in Example 1 to produce a laminated glass.

Example 3 A completely hydrogenated rosin was added to 100 parts by weight of a carboxyl modified product of a saponified ethylene-vinyl acetate copolymer (melt index: 20 g / 10 min, Dumilan C-1550, manufactured by Takeda Pharmaceutical Co., Ltd.). Pentaerythritol ester 7
Parts by weight and 4 parts by weight of dioctyl phthalate and γ-
1 part by weight of glycidoxypropyltrimethoxysilane is uniformly dispersed and formed into a film having a thickness of 0.25 mm. The film was treated in the same manner as in Example 1 to produce a laminated glass.

Example 4 A fully hydrogenated rosin was added to 100 parts by weight of a carboxyl modified product of a saponified ethylene-vinyl acetate copolymer (melt index: 20 g / 10 min, Dumilan C-1550, manufactured by Takeda Pharmaceutical Co., Ltd.). Pentaerythritol ester 1
5 parts by weight, 7 parts by weight of dioctyl phthalate and γ
1 part by weight of glycidoxypropyltrimethoxysilane is uniformly dispersed and formed into a film having a thickness of 0.25 mm. The film was treated in the same manner as in Example 1 to produce a laminated glass.

Example 5 A completely hydrogenated rosin was added to 100 parts by weight of a carboxyl modified product of a saponified ethylene-vinyl acetate copolymer (melt index: 20 g / 10 min, Dumilan C-1550, manufactured by Takeda Pharmaceutical Co., Ltd.). Pentaerythritol ester 2
0 parts by weight, 10 parts by weight of dioctyl phthalate and 1 part by weight of γ-glycidoxypropyltrimethoxysilane are uniformly dispersed and formed into a film having a thickness of 0.25 mm. The film was treated in the same manner as in Example 1 to produce a laminated glass.

Comparative Example 1 A carboxyl modified product of a saponified ethylene-vinyl acetate copolymer (melt index: 20 g / 10 min, Dumilan C-1550, manufactured by Takeda Pharmaceutical Co., Ltd.) was prepared by adding 100 parts by weight to a 0.25 mm thick plate. Form into a film. The film was treated in the same manner as in Example 1 to produce a laminated glass. Comparative Example 2 100 parts by weight of a carboxyl modified product of a saponified ethylene-vinyl acetate copolymer (melt index: 20 g / 10 min, Dumilan C-1550, manufactured by Takeda Pharmaceutical Co., Ltd.) was added to 100 parts by weight of a completely hydrogenated rosin pentaerythritol ester. 1
0 parts by weight are uniformly dispersed and formed into a film having a thickness of 0.25 mm. The film was treated in the same manner as in Example 1 to produce a laminated glass.

Comparative Example 3 Ethylene-vinyl acetate copolymer (melt index 3
5 g of dioctyl phthalate is uniformly dispersed in 100 g of Evaflex EV150 (manufactured by Mitsui-DuPont Polychemical Co., Ltd.) at 0 g / 10 min, and formed into a film having a thickness of 0.25 mm. The film was treated in the same manner as in Example 1 to produce a laminated glass. Comparative Example 4 Ethylene-vinyl acetate copolymer (melt index 3
In 0 g / 10 minutes, 100 parts by weight of Evaflex EV150 (manufactured by Du Pont-Mitsui Polychemicals), 5 parts by weight of dioctyl phthalate and 1 part by weight of γ-glycidoxypropyltrimethoxysilane were uniformly dispersed. Into a film having a thickness of 0.25 mm. The film was treated in the same manner as in Example 1 to produce a laminated glass.

The transparency, glazing resistance, and plasticity of the obtained laminated glass were measured by the following methods and criteria. The results are shown in [Table 1]. Transparency test The measurement of the total light transmittance and the measurement of haze were performed according to the test method specified in JISR3212. ：: No fogging (same as glass alone) ：: Fogging is observed depending on the angle and the degree of hit by the light beam. Δ: Clouding is observed. Glazing resistance gasket test A glazing gasket made of polyvinyl chloride containing about 40% of dioctyl phthalate (DOP) as a plasticizer was attached to a cut end of a laminated glass of 100 mm x 50 mm so as to be in contact with the interlayer. The appearance (whether peeled) of the laminated glass to which the glazing gasket was attached after 50 ° C. × 4 weeks was observed. ：: No peeling. ×: Peeling occurred. Plasticizer resistance test Dioctyl phthalate (DOP) as a plasticizer was applied to a cut end of a 100 mm x 50 mm laminated glass so as to be in contact with the intermediate film. The appearance (whether or not peeled off) of the laminated glass coated with the plasticizer after 4 weeks at 50 ° C. was observed. ○: No peeling ×: Peeling

[0019]

[Table 1] As is clear from Table 1, the interlayer film of the present invention has excellent transparency, glazing resistance, and plasticity resistance.

[0020]

The laminated glass using the adhesive interlayer of the present invention adheres well to glass, polyester films, polarizing films, acrylic plates, polycarbonate plates and the like. Also,
Since it is excellent in plasticizer resistance, even when a buffer material containing a plasticizer is used, it is possible to obtain a laminated glass that is hardly peeled off, has excellent durability, and has the same transparency as glass.

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Claims (3)

[Claims] 1. A partially saponified ethylene-vinyl acetate copolymer or 100 parts by weight of an acid-modified product thereof, and rosins 2 to 2
An adhesive interlayer for laminated glass comprising 0 parts by weight and 0.5 to 10 parts by weight of a plasticizer. 2. A silane coupling agent of 0.05 to 3
2. The adhesive interlayer film for laminated glass according to claim 1, comprising parts by weight. 3. A laminated glass laminated using the adhesive interlayer film for laminated glass according to claim 1 or 2.